Abstract
Barrelene, H–C(CH=CH)3C–H, is an unsaturated polycyclic hydrocarbon containing three isolated double bonds in a non-planar arrangement. We have studied the transmission of field effects through the barrelene framework by analyzing the small structural changes occurring in the phenyl group of many Ph–C(CH=CH)3C–X molecules, where X is a variable substituent. Molecular geometries have been determined by quantum chemical calculations at the HF/6-31G* and B3LYP/6-311++G** levels of theory. Comparison with the results obtained for the corresponding saturated molecules, the bicyclo[2.2.2]octane derivatives Ph–C(CH2–CH2)3C–X, reveals a small, but significant, field-induced π-polarization of the barrelene cage, especially when the remote substituent is a charged group. Additional evidence of π-polarization is obtained by comparing the electric dipole moments of the two sets of uncharged molecules. The structural variation of the barrelene cage caused by the variable substituent in Ph–C(CH=CH)3C–X molecules has also been investigated. It is much larger than that of the phenyl group and depends primarily on the electronegativity of the substituent. Particularly pronounced is the concerted variation of the non-bonded distance between the bridgehead carbons of the cage, r(C···C) BARR1 , and the average of the three C–C–C angles at the cage carbon bonded to the variable substituent, α BARR1 . A scattergram of r(C···C) BARR1 versus the corresponding parameter for bicyclo[2.2.2]octane derivatives, r(C···C) BCO1 , shows that the variation of r(C···C) BARR1 becomes gradually less pronounced than that of r(C···C) BCO1 as the electronegativity of the substituent increases.
Similar content being viewed by others
References
Campanelli AR, Domenicano A, Ramondo F (2006) J Phys Chem A 110:10122–10129
Campanelli AR, Domenicano A, Piacente G, Ramondo F (2010) J Phys Chem A 114:5162–5170
Campanelli AR, Domenicano A, Ramondo F (2011) Struct Chem 22:449–457
Campanelli AR, Domenicano A (2014) Struct Chem 25:691–698
Campanelli AR, Domenicano A, Ramondo F (2012) J Phys Chem A 116:8209–8217
Campanelli AR, Domenicano A (2013) Struct Chem 24:867–876
Campanelli AR (2013) Struct Chem 24:859–866
Campanelli AR, Domenicano A (2015) Struct Chem 26:1259–1271
Campanelli AR, Domenicano A, Hnyk D (2015) J Phys Chem A 119:205–214
Zimmerman HE, Paufler RM (1960) J Am Chem Soc 82:1514–1515
Zimmerman HE, Grunewald GL, Paufler RM, Sherwin MA (1969) J Am Chem Soc 91:2330–2338
Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashy R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas O, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2010) Gaussian 09, Revision C.01. Gaussian, Inc., Wallingford
Sałek P, Helgaker T, Vahtras O, Ågren H, Jonsson D, Gauss J (2005) Mol Phys 103:439–450
Soscún H, Castellano O, Bermúdez Y, Toro C, Cubillán N, Hinchliffe A, Phu XN (2006) Int J Quantum Chem 106:1130–1137
Campanelli AR, Domenicano A, Ramondo F (2003) J Phys Chem A 107:6429–6440
Campanelli AR, Domenicano A, Macchiagodena M, Ramondo F (2011) Struct Chem 22:1131–1141
Campanelli AR, Domenicano A, Ramondo F, Hargittai I (2004) J Phys Chem A 108:4940–4948
Domenicano A, Murray-Rust P, Vaciago A (1983) Acta Crystallogr B 39:457–468
Topsom RD (1976) Prog Phys Org Chem 12:1–20
Reynolds WF (1983) Prog Phys Org Chem 14:165–203
Taft RW, Topsom RD (1987) Prog Phys Org Chem 16:1–83
Böhm S, Exner O (2004) J Mol Struct (Theochem) 682:171–177
Acknowledgments
This work was supported by the CINECA Supercomputing Center, Bologna, with Project IsC10_DYNGEO_E, and by the Department of Chemistry, Sapienza - University of Rome, through the Supporting Research Initiative 2013.
Author information
Authors and Affiliations
Corresponding authors
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Campanelli, A.R., Domenicano, A. & Ramondo, F. Field-induced π-polarization in barrelene derivatives: a computational study based on structural variation. Struct Chem 28, 617–624 (2017). https://doi.org/10.1007/s11224-016-0829-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11224-016-0829-3